Keto-Enol Tautomeric Equilibrium of Acetylacetone Solution Confined in Extended Nanospaces

We aim to clarify the effects of size confinement, solvent, and deuterium substitution on keto-enol tautomerization of acetylacetone (AcAc) in solutions confined in 10-100 nm spaces (i.e., extended nanospaces) using (1)H NMR spectroscopy. The keto-enol equilibrium constants of AcAc (K(EQ) = [keto]/[enol]) in various solvents confined in extended nanospaces of 200-3000 nm were examined using the area ratios of -CH3 peaks in keto to enol forms. The results showed that the keto form of AcAc in hydrogen-bonded solvents such as water and ethanol increased drastically with decreasing space sizes below about 500 nm, but the size confinement did not induce equilibrium shifts in aprotic solvents such as DMSO. The magnitudes of K(EQ) enhancement were well correlated with solvent proton donicity. It followed from the determination of thermodynamic parameters that the stabilization of intermolecular interactions between protons in water and carbonyl oxygen (C═O) in the keto form of AcAc were promoted by size-confinement, and that the keto form could be energetically and structurally favored in extended nanospaces vis-à-vis the bulk space. Furthermore, the measurements of deuterium dependence of the K(EQ) values verified that the nanoconfinement-induced shifts of keto-enol tautomerization of AcAc are attributable to high proton mobility via a proton hopping mechanism of the confined water.